Vinyl chloride resin compositions

ABSTRACT

The present invention provides a vinyl chloride resin composition having an elevated heat distortion temperature, comprising 
     ]I[ [A] a vinyl chloride resin, and 
     [II] [B] cycloolefin ring opening polymer or copolymer formed by ring opening polymerization of a cycloolefin represented by the formula [I], or a hydrogenated product thereof, and/or 
     [C] a cycloolefin random copolymer of ethylene and a cycloolefin represented by the formula [I], said copolymer having an intrinsic viscosity [η], as measured in decalin at 135° C., of 0.05 to 10 dl/g and a glass transition temperature Tg of at least 70° C., ##STR1##  wherein n is 0 or 1, and m is 0 or a positive integer.

FIELD OF THE INVENTION

The present invention relates to vinyl chloride resin compositions, andparticularly to vinyl chloride resin compositions having an elevatedheat distortion (deflection) temperature by incorporation of acycloolefin polymer thereinto to improve the properties of the moldedarticles.

BACKGROUND OF THE INVENTION

Vinyl chloride resins such as polyvinyl chloride, copolymers of vinylchloride and other monomers, or vinyl chloride resin derivatives, forexample, halogenated polyvinyl chloride (these resins being merelyreferred to vinyl chloride resins hereinafter) have excellent scratchresistance, flame retarding properties, chemical resistance and electriccharacteristics, and show a decreased mold shrinkage factor. Vinylchloride resins are therefore used as material for various moldedarticles. Molded articles made of vinyl chloride resins are used undersuch peculiar circumstances as water tanks of electric irons, electronicoven parts, printed circuit boards, conductive sheets and helmets.

However, conventional vinyl chloride resins have a problem that moldedproducts obtained therefrom are restricted in their use due to their lowheat distortion temperature, although they are excellent in flameretarding properties, chemical resistance, a low mold shrinkage factor,etc.

An object of the present invention is to provide vinyl chloride resincompositions having an elevated heat distortion (deflection) temperatureor an elevated heat deformation temperature while excellent propertiesof conventional vinyl chloride resin compositions, such as flameretarding properties and a low mold shrinkage factor, are maintained.

DISCLOSURE OF THE INVENTION

A vinyl chloride resin composition according to the present inventioncomprises

[I] [A] a vinyl chloride resin and

[II] [B] a cycloolefin ring opening polymer or copolymer formed by ringopening polymerization of a cycloolefin represented by the followingformula [I], or a hydrogenated product thereof, and/or

[C] a cycloolefin random copolymer of ethylene and a cycloolefinrepresented by the following formula [I], said random copolymer havingan intrinsic viscosity [η], as measured at 135° C. in decalin, of 0.05to 10 dl/g and a glass transition temperature (Tg) of at least 70° C.,##STR2## wherein n is 0 or 1, m is 0 or a positive integer, R¹ -R¹⁸ areeach independently an atom or a group selected from the group consistingof hydrogen, halogen and hydrocarbon groups, R¹⁵ -R¹⁸, linked together,may form a monocyclic ring or polycyclic ring which may have a doublebond, R¹⁵ and R¹⁶ or R¹⁷ and R¹⁸ may form together an alkylidene group.

The vinyl chloride resin compositions according to the present inventioncomprise a vinyl chloride resin [A], and a specific cycloolefin ringopening polymer or copolymer, or a hydrogenated product thereof [B],and/or a specific cycloolefin random copolymer [C]. Accordingly, itbecomes possible to elevate the heat distortion temperature thereof, andimprove the plastication and decomposition temperature thereof while theexcellent flame retarding properties and small mold shrinkage factorsare maintained.

The excellent properties of the vinyl chloride resin [A] are notimpaired even when the vinyl chloride resin contains the cycloolefinring opening polymer or copolymer, or hydrogenated product thereof [B]and/or the cycloolefin random copolymer [C].

DETAILED DESCRIPTION OF THE INVENTION

The vinyl chloride resin compositions according to the present inventionare concretely illustrated below.

The present invention is based on the finding that the heat distortiontemperature of the vinyl chloride resin [A] is significantly increasedwhen the resin [A] contains the cycloolefin ring opening polymer orcopolymer, or hydrogenated product thereof [B] and/or the cycloolefinrandom copolymer [C] ([B] and [C] may be generally referred tocycloolefin copolymers hereinafter).

The vinyl chloride resin composition according to the present inventioncomprises

[I] a vinyl chloride resin [A], and

[II] a cycloolefin ring opening polymer or copolymer formed by ringopening polymerization of a cycloolefin represented by the followingformula [I], or a hydrogenated product thereof [B], and/or

a cycloolefin random copolymer of ethylene and a cycloolefin representedby the following formula [I] [C], ##STR3## wherein n is 0 or 1, m is 0or a positive integer, R¹ -R¹⁸ are each independently an atom or a groupselected from the group consisting of hydrogen, halogen and hydrocarbongroups, R¹⁵ -R¹⁸, linked together, may form a monocyclic ring or apolycyclic ring which may have a double bond, R¹⁵ and R¹⁶, or R¹⁷ andR¹⁸ may form together an alkylidene group.

The vinyl chloride resin compositions containing a cycloolefin polymerhave an elevated heat distortion temperature (HDT measured by the heatdeflection method according to ASTM D 648) while maintaining flameretarding properties, etc. compared with singly used conventional vinylchloride resins. The comparison of Examples 1 to 3 and ComparativeExample 1, which are described later, shows that the vinyl chlorideresin in Comparative Example 1 containing no cycloolefin copolymerexhibits a lower heat distortion temperature than that of the vinylchloride resin compositions in Examples 1 to 3 containing a cycloolefincopolymer. Further, the resin compositions in Examples 1 to 3 have thesame excellent tensile strength at break and flame retarding propertiesas the resin in Comparative Example 1, which shows the physicalproperties of the vinyl chloride resin are maintained in the vinylchloride resin compositions according to the present invention.

In addition, the vinyl chloride resins herein are not restricted topolyvinyl chloride, but include copolymers of vinyl chloride and otherpolymerizable monomers such as vinyl acetate and vinylidene chloride,vinyl chloride-grafted products such as a vinyl chloride-graftedethylene/vinyl acetate copolymer, and derivatives of chlorinated vinylchloride resins obtained by chlorinating polyvinyl chloride.

VINYL CHLORIDE RESINS

Typical example of the vinyl chloride resin [A] used in the vinylchloride resin compositions according to the present invention ispolyvinyl chloride, but is not restricted to the polyvinyl chloride. Thevinyl chloride resin [A] may be a copolymer of vinyl chloride and otherpolymerizable monomers, or a modified product derived from vinylchloride.

(1) Examples of the copolymer of vinyl chloride include vinylchloride/vinyl acetate copolymer, vinyl chloride/vinylidene chloridecopolymer, vinyl chloride/(meth)acrylic acid copolymer, vinylchloride/(meth)acrylate copolymer, vinyl chloride/maleic acid copolymer,vinyl chloride/maleate copolymer, vinyl chloride/acrylonitrile copolymerand vinyl chloride/α-olefin random copolymer (α-olefin includingethylene and propylene).

(2) Examples of the vinyl chloride-grafted product include vinylchloride-grafted products of ethylene/vinyl acetate copolymer andbutadiene/acrylate copolymer.

Furthermore, the vinyl chloride resin [A] includes modified (co)polymersprepared by grafting the (co)polymers described in (1) and (2) with avinyl monomer such as styene and methacrylate.

In addition, the modified product derived from polyvinyl chlorideincludes chlorinated vinyl chloride resin obtained by chlorinatingpolyvinyl chloride.

The vinyl chloride resin [A] has a melt flow rate, as measured at 190°C. under a load of 2.16 kg, of 0.1 to 500 g/10 min, preferably 1 to 100g/10 min and especially 5 to 50 g/10 min.

The vinyl chloride resin [A] has an average polymerization degree of 200to 5000, preferably 300 to 4000 and especially 400 to 3000.

The vinyl chloride resin [A] has, under a load of 18.6 kg, a heatdistortion temperature of 40° to 90° C., preferably 50° to 80° C.

The vinyl chloride resin [A] has a glass transition temperature (Tg) of40° to 90° C., preferably 50° to 80° C.

CYCLOOLEFIN POLYMER CONTAINED IN VINYL CHLORIDE RESIN

The cycloolefin polymers used in the vinyl chloride resin compositionsof the invention include

[B] a ring opening polymer or copolymer of a cycloolefin represented bythe aforementioned formula [I], or a hydrogenated product thereof, and

[C] a cycloolefin random copolymer obtained by addition polymerizationof ethylene and a cycloolefin represented by the aforementioned formula[I].

In the above-mentioned formula [I], n is 0 or 1, and m is 0 or apositive integer, preferably 0 to 3.

R¹ -R¹⁸ each independently represent an atom or a group selected fromthe group consisting of hydrogen, halogen and hydrocarbon groups. Thehalogen herein includes a fluorine atom, a chlorine atom, a bromine atomand an iodine atom. The hydrocarbon groups each include usually an alkylgroup of 1 to 10 carbon atoms and a cycloalkyl group of 5 to 15 carbonatoms. Concrete examples of the alkyl group include methyl, ethyl,isopropyl, isobutyl, n-amyl, neopentyl, n-hexyl, n-octyl, n-decyl and2-ethylhexyl. Concrete examples of the cycloalkyl group includecyclohexyl, methylcyclohexyl and ethylcyclohexyl.

Furthermore, in the above-mentioned formula [I], R¹⁵ -R¹⁸, linked withone another (together), may form a monocyclic ring or a polycyclic ringwhich may have a double bond.

In addition, R¹⁵ and R¹⁶, or R¹⁷ and R¹⁸ may form an alkylidene group.The alkylidene group is usually one having 2 to 10 carbon atoms.Concrete examples of the alkylidene group include ethylidene,propylidene, isopropylidene, butylidene and isobutylidene.

In the aforementioned formula [I], R¹⁵ -R¹⁸, linked together, may form amonocyclic ring or a polycyclic ring which may have a double bond.

The cycloolefin represented by the formula [I] can be easily prepared bycondensation reaction through Diels-Alder reaction of cyclopentadieneswith corresponding olefins or cycloolefins.

Concrete examples of the cycloolefin represented by the above-mentionedformula [I] include the following compounds.

Bicyclo [2,2,1]hept-2-ene derivatives such as those mentioned below.##STR4##

Tetracyclo[4,4,0,1².5,1⁷.10 ]-3-dodecene derivatives such as thosedescribed below. ##STR5##

Hexacyclo[6,6,1,1³.6, 1¹⁰.13,0².7,0⁹.14 ]-4-heptadecene derivatives suchas those mentioned below. ##STR6##

Octacyclo[8,8,0,1².9,1⁴.7,1¹¹.18,1¹³.16,0³.8,0.sup.12.17 ]-5-docosenederivatives such as those mentioned below. ##STR7##

Pentacyclo[6,6,1,1³.6,0².7,0⁹.14 ]-4-hexadecene derivatives such asthose mentioned below. ##STR8##

Heptacyclo-5-eicosene derivatives or heptacyclo-5-heneicosenederivatives such as those mentioned below. ##STR9##

Tricyclo[4,3,0,1².5 ]-3-decene derivatives such as those mentionedbelow. ##STR10##

Tricyclo[4,4,0,1².5 ]-3-undecene derivatives such as those mentionedbelow. ##STR11##

Pentacyclo[6,5,1,1³.6,0².7,0⁹.13 ]-4-pentadecene derivatives such asthose mentioned below. ##STR12##

Pentacyclo[4,7,0,1².5,0⁸.13,1⁹.12 ]-3-pentadecene derivatives such asthose mentioned below. ##STR13##

Heptacyclo[7,8,0,1³.6,0².7,1¹⁰.17,0¹¹.16,1¹².15 ]-4-eicosene derivativessuch as those mentioned below. ##STR14##

Nonacyclo[9,10,1,1⁴.7,0³.8,0².10,0¹².21,1¹³.20,0.sup.14.19,1¹⁵.18]-5-pentacosene derivatives such as those mentioned below. ##STR15##

Subsequently,

[B] the cycloolefin ring opening polymer or copolymer, or hydrogenatedproduct thereof and

[C] the cycloolefin random copolymer [C] used in the resin compositionsaccording to the present invention are illustrated below in detail.

[B] CYCLOOLEFIN RING OPENING POLYMER OR COPOLYMER, OR HYDROGENATEDPRODUCT THEREOF

The cycloolefin ring opening polymer and ring opening copolymer used inthe invention can be obtained by ring opening polymerization of acycloolefin represented by the formula [I] mentioned above in thepresence of a catalyst comprising, for example, a halide, a nitride oran acetylacetone compound of a metal such as ruthenium, rhodium,palladium, osmium, indium or platinum, and a reducing agent such as analcohol. The resultant product may be a homopolymer or a copolymer. Forexample, the resultant homopolymer may be a polymerization product of1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalenes, or acopolymerization product of said naphthalenes and norbornenes such asbicyclo[2.2.1]hept-2-ene.

The double bonds remaining in the cycloolefin ring opening polymer andring opening copolymer as described above can be easily hydrogenated inthe presence of a hydrogenation catalyst. The resultant hydrogenatedproduct provides molding material which is more excellent in heatstability and weathering resistance.

Any of heterogeneous catalysts or homogeneous catalysts generally usedfor hydrogenation of olefins may be used as the hydrogenation catalysts.

Useful heterogeneous catalysts include catalysts in which a metal suchas nickel, palladium or platinum, or a catalyst prepared by supportingthese metals on a carrier such as carbon, silica, diatomaceous earth,alumina or titanium oxide. Concrete examples of the heterogeneouscatalyst include nickel/silica, nickel/diatomaceous earth,palladium/carbon, palladium/silica, palladium/diatomaceous earth andpalladium/alumina.

Useful homogeneous catalysts include catalysts containing a Group VIIImetal in the periodic table. Concrete examples of the catalysts includecatalysts comprising nickel or cobalt compounds, and organometalcompounds containing metals belonging to Group I to III in the periodictable such as nickel and cobalt, for example, nickelnaphthenate/triethylamine, naphthenic acid n-butyllithium naphthenateand acetylacetonatonickel/triethylaluminum, and rhodium compounds.

The hydrogenation reaction can be carried out in a homogeneous or aheterogeneous system, depending on the type of the catalysts.

The hydrogen gas pressure in the hydrogenation is usually 1 to 150atmospheric pressure, and the reaction temperature is usually 0 to 100°C., preferably 20° to 100° C.

The hydrogenation ratio can be freely adjusted by changing the hydrogenpressure, reaction temperature, reaction time, catalyst concentration,etc. However, the hydrogenated products used in the invention have ahydrogenation ratio of the double bonds present in the originalnon-hydrogenated polymer or copolymer of preferably at least 50%, morepreferably at least 80% and especially at least 90%. Especially thosehydrogenated products having a hydrogenation ratio exceeding 90% come toexhibit a solubility parameter (SP) range different from that of theresin before hydrogenation. Resin compositions excellent in solventresistance can be obtained from such a resin.

Furthermore, in the preparation of the ring opening polymers, ringopening copolymers or hydrogenated products thereof as mentioned abovein the invention, cycloolefins other than those represented by theformula [I] can be copolymerized. Such cycloolefins include

cyclobutene,

cyclopentene,

cyclohexene,

3,4-dimethylcyclohexene,

3-methylcyclohexene,

2-(2-methylbutyl)-1-cyclohexene,

2,3,3a,7a-tetrahydro-4,7-methano-1H-indene and

3a,5,6,7a-tetrahydro-4,7-methano-1H-indene. These other cycloolefins canbe used singly or in combination, and are usually used in an amount of 0to 20 mol%.

When the ring opening polymerization or copolymerization is conducted asdescribed above, the cycloolefin such as represented, for example, bythe formula [I] opens its ring, and at least part of the products areconsidered to have a structure represented by the following formula [II]##STR16## wherein m, n and R¹ -R¹⁸ are as defined in the aforementionedformula [I].

The hydrogenated product obtained by hydrogenating double bonds isconsidered to have a structure represented, for example, by the formula[III] ##STR17## wherein m, n and R¹ -R¹⁸ are as defined in theaforementioned formula [I].

The ring opening polymers and copolymers, and hydrogenated productsthereof can be used singly or in combination in the present invention.Moreover, it is preferable that these ring opening polymers, ringopening copolymers or hydrogenated products thereof are modified withunsaturated carboxylic acids such as maleic anhydride.

These cycloolefin ring opening polymers, ring opening copolymers orhydrogenated products thereof [B] have an intrinsic viscosity [η] ofdesirably 0.1 to 7 dl/g as measured in decalin at 135° C. and a meltflow rate of desirably 0.01 to 150 g/10 min as measured at 260° C. undera load of 2.16 kg.

CYCLOOLEFIN RANDOM COPOLYMER [C]

The cycloolefin random copolymer [C] contained in the resin compositionsof the invention comprises, as essential structural units, structuralunits derived from ethylene and those derived from the aforementionedcycloolefin. The cycloolefin random copolymer [C] may also contain othercopolymerizable unsaturated monomer structural units if desired, so longas these other structural units do not impair the object of theinvention. Unsaturated monomers which may be copolymerized includeconcretely propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene,1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and1-eicosene. Of these, an α-olefin having 3 to 20 carbon atoms ispreferable. Moreover, cycloolefins and cyclodienes such as norbornene,ethylidenenorbornene and dicyclopentadiene may also be used. Theseunsaturated monomer structural units may be contained in the resultingrandom copolymer in a molar amount less than that of the structuralunits derived from ethylene.

The cycloolefin random copolymer [C] contained in the resin compositionsaccording to the present invention comprises structural units derivedfrom ethylene in an amount of 40 to 85 mol%, preferably 50 to 75 mol%.The copolymer [C] comprises structural units derived from thecycloolefin in an amount of 15 to 60 mol%, preferably 25 to 50 mol%. Inthe present invention, structural units derived from ethylene and thosederived from the cycloolefin are randomly arranged to form asubstantially linear cycloolefin random copolymer. The fact that theaforementioned cycloolefin random copolymer is substantially linear andhas no gel-like crosslinking structure can be ascertained by observingcomplete dissolution of the copolymer in decalin at 135° C.

The cycloolefin random copolymer [C] contained in the resin compositionsof the invention has an intrinsic viscosity [η], as measured in decalinat 135° C., of 0.05 to 10 dl/g, preferably 0.08 to 5 dl/g.

Furthermore, the cycloolefin random copolymer [C] contained in the resincompositions of the invention has a melt flow rate of 0.01 to 150 g/10min as measured at 260° C. under a load of 2.16 kg.

Still furthermore, the cycloolefin random copolymer [C] contained in thecycloolefin resin compositions of the invention has a softeningtemperature (TMA), as measured by a thermomechanical analyzer, of atleast 70° C., preferably 90° to 250° C. and especially 100° to 200° C.

The cycloolefin random copolymer [C] contained in the resin compositionsof the invention has a glass transition temperature (Tg) of usually 50°to 230° C., preferably 70° to 210° C.

The cycloolefin random copolymer [C] contained in the resin compositionsof the invention has a crystallinity, as measured by X-ray diffraction,of 0 to 10%, preferably 0 to 7% and especially 0 to 5%.

As the cycloolefin random copolymer [C] contained in the resincompositions according to the present invention, only the copolymershaving physical properties in the above-mentioned range may be used.However, those having physical properties outside the above-mentionedrange may also be partly contained. In this case, when the physicalproperties of the cycloolefin random copolymer [C] as a whole lie in theabove-mentioned range, the random copolymer [C] can be used.

Such a cycloolefin random copolymer [C] can be manufactured bycopolymerizing ethylene, cycloolefin, and if necessary other α-olefin ina hydrocarbon solvent in the presence of a catalyst formed from ahydrocarbon-soluble vanadium compound and a halogen-containingorganoaluminum compound.

The hydrocarbon solvents used herein include aliphatic hydrocarbons,alicyclic hydrocarbons and aromatic hydrocarbons. Moreover, monomerswhich are in a liquid form at the reaction temperature may be used asreaction solvents. These solvents may be used singly or in combination.

Useful vanadium compounds used as catalysts in the reaction includethose represented by the general formula VO(OR)_(a) V_(b) or V(OR)_(c)X_(d), wherein R is a hydrocarbon group, 0≦a≦3, 0≦b ≦3, 2≦a+b≦3, 0≦c≦4,0≦d≦4, and 3≦c+d≦4.

More concretely, these vanadium compounds include

VOCl₃,

VO(OC₂ H₅)Cl₂,

VO(OC₂ H₅)₂ Cl,

VO(O-iso-C₃ H₇)Cl₂,

VO(O-n-C₄ H₉)Cl₂,

VO(OC₂ H₅)₃,

VOBr₂,

VCl₄,

VOCl₂,

VO(O-n-C₄ H₉)₃, and

VCl₃ ·2OC₈ H₁₇ OH. These vanadium compounds may be used singly or incombination.

Adducts of the vanadium compounds represented by the above-mentionedformula and electron donors may also be used in place of such vanadiumcompounds as mentioned above.

Examples of the electron donors which form adducts with the vanadiumcompounds mentioned above include oxygen-containing electron donors suchas alcohols, phenols, ketones, aldehydes, carboxylic acids, esters oforganic acids or inorganic acids, ethers, acid amides, acid anhydridesand alkoxysilanes, and nitrogen-containing electron donors such asammonia, amines, nitriles and isocyanates.

Useful organoaluminum compounds which can be used as catalysts with thevanadium compounds as mentioned above include those having in themolecule at least one Al-C bond.

Examples of the organoaluminum compounds usable in the invention includeorganoaluminum compounds represented by the formula

    R.sup.19.sub.e Al(OR.sup.20).sub.f H.sub.g X.sub.h

wherein R¹⁹ and R²⁰, which may be the same or different, are each ahydrocarbon group of 1 to 15 carbon atoms, preferably 1 to 4 carbonatoms, X is halogen, 0≦e≦3, 0≦f<3, 0≦g<3, 0≦h<3, and e+f+g+h=3, andcomplex alkylation compounds of metals belonging to Group I of theperiodic table and aluminum, represented by the formula

    M.sup.1 AlR.sup.21.sub.4

wherein M¹ is Li, Na or K, R²¹, which may be the same or different, areeach a hydrocarbon group of 1 to 15 carbon atoms, preferably 1 to 4carbon atoms.

In the aforementioned reaction system, the vanadium compounds are usedin an amount of usually 0.01 to 5 g atom/1, preferably 0.05 to 3 gatom/1 in terms of vanadium. Moreover, the organoaluminum compounds areused so that the ratio (Al/V) in the polymerization system of aluminumatoms to vanadium atoms is at least 2, preferably 2 to 50 and especially3 to 20.

The cycloolefin random copolymer [C] contained in the resin compositionsof the invention can be prepared, for example, by following theprocedures proposed by the present applicant in Japanese Patent L-O-PNos. 168708/1985, 120816/1986, 115912/1986, 115916/1986, 271308/1986,272216/1986, 252406/1987 and 252407/1987, and suitably selecting thereaction conditions.

In the cycloolefin random copolymer [C] as described above, thestructural unit derived from a cycloolefin represented by theabove-mentioned formula [I] is considered to form a recurring unit of astructure represented by the formula [IV] ##STR18## wherein n, m and R¹-R¹⁸ are as defined in the aforementioned formula [I].

Furthermore, in the present invention, it is preferable that thecycloolefin ring opening polymer or copolymer, or hydrogenated productthereof [B] as described above, or the cycloolefin random copolymer [C]([B] and [C] being generally abbreviated to cycloolefin polymer) ismodified with an unsaturated carboxylic acid such as maleic anhydride.Such a modified product can be manufactured by reacting the cycloolefinpolymer as described above with an unsaturated carboxylic acid or ananhydride thereof, or a derivative of the unsaturated carboxylic acidsuch as an alkyl ester thereof. The modified cycloolefin polymercontains structural units derived from a modifier in an amount ofusually not greater than 0.001 to 5% by weight. The modified cycloolefinpolymer may be prepared by graft polymerizing a modifier to thecycloolefin polymer so that a desired modification ratio is obtained, orby preparing a modified product of the cycloolefin polymer having a highgraft ratio at first, and then mixing the modified product with theunmodified cycloolefin polymer.

In the vinyl chloride resin compositions of the invention, the ratio byweight of the total amount of the cycloolefin ring opening polymer orcopolymer, or hydrogenated product thereof [B] and the cycloolefinrandom copolymer [C] ([B] +[C]) to the weight of the vinyl chlorideresin [A] {([B]+[C])/[A])} is 98/2 to 2/98, preferably 95/5 to 5/95.

OTHER ADDITIVES

In addition to the above-mentioned components [A], [B] and [C], theresin compositions of the invention may contain a rubber component forimproving the impact strength thereof. It may also contain heatstabilizers, weathering stabilizers, antistatic agents, slip agents,anti-blocking agents, antihaze agents, lubricants, dyes, pigments,natural oil, synthetic oil, wax, etc. These additives are used insuitable amounts. Concrete examples of stabilizers to be used asoptional components include phenolic antioxidants such astetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane,alkyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and2,2'-oxamidobis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate,zinc stearate, calcium stearate, and aliphatic acid esters of polyhydricalcohols such as glycerin monostearate, glycerin monolaurate, glycerindistearate, pentaerythritol monostearate, pentaerythritol distearate andpentaerythritol tristearate.

Useful stabilizers include lead salts, metallic soaps and organotincompounds. Concrete examples of the lead salts include white lead,tribasic lead sulfate, dibasic lead phosphite, dibasic lead phthalate,lead silicate or coprecipitates of these compounds with silica gel.

The metallic soaps concretely include salts of organic acids such asstearic acid, 12-hydroxystearic acid, lauric acid, ricinoleic acid,naphthenic acid and 2-ethylhexanoic acid and metals such as lead,cadmium, barium, zinc and calcium.

Useful organotin compounds include concretely dibutyltin laurate,dibutyltin maleate and dibutyltin mercaptide.

These stabilizers may be used singly or in combination. One of theexamples of the combination is a combination oftetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane,zinc stearate, glycerin monostearate and a lead salt.

In the present invention, the use of phenolic antioxidants and aliphaticacid esters of polyhydric alcohols in combination is particularlypreferred. As the aliphatic acid ester of a polyhydric alcohol, an esterin which the alcoholic hydroxy group of the alcohol (at least trihydric)is partially esterified is preferred.

Concrete examples of the aliphatic acid ester of a polyhydric alcoholinclude aliphatic acid esters of glycerin such as glycerin monostearate,glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate,glycerin distearate and glycerin dilaurate, and aliphatic acid esters ofpentaerythritol such as pentaerythritol monostearate, pentaerythritolmonolaurate, pentaerythritol dilaurate, pentaerythritol distearate andpentaerythritol tristearate.

Such phenolic antioxidants are used in an amount, based on 100 parts byweight of the vinyl chloride composition, of 0.01 to 10 parts by weight,preferably 0.05 to 3 parts by weight and especially 0.1 to 1 part byweight. The aliphatic acid esters of polyhydric alcohols are used in anamount, based on 100 parts by weight of the resin composition, of 0.01to 10 parts by weight, preferably 0.05 to 3 parts by weight.

The vinyl chloride resin compositions of the invention may beincorporated with fillers, so long as the incorporation does not impairthe object of the invention, such as silica, diatomaceous earth,alumina, titanium oxide, magnesium oxide, pumice powder, pumiceballoons, aluminum hydroxide, magnesium hydroxide, basic magnesiumcarbonate, dolomite, calcium sulfate, potassium titanate, bariumsulfate, calcium sulfite, talc, clay, mica, asbestos, glass fibers,glass flakes, glass beads, calcium silicate, montmorillonite, bentonite,graphite, aluminum powder, molybdenum sulfide, boron fibers, siliconcarbide fibers, polyethylene fibers, polypropylene fibers, polyesterfibers and polyamide fibers.

The vinyl chloride resin compositions of the invention may also beincorporated with olefin resin (including rubber) derived from ahydrocarbon having one or more of unsaturated bonds.

Such polymers concretely include

homopolymers such as polyethylene, polypropylene, polyisobutylene,polymethylbutene-1, poly-4-methylpentene-1, polybutene-1, polyisoprene,polybutadiene and polystyrene;

copolymers such as ethylene/propylene copolymer, propylene/butene-1copolymer, propylene/isobutylene copolymer, styrene/isobutylenecopolymer, styrene/butadiene copolymer and ethylene/propylene/dienecopolymer, e.g., ethylene/propylene/hexadiene copolymer,ethylene/propylene/cyclopentadiene copolymer andethylene/propylene/ethylidenenorbornene copolymer, or

blends, grafted polymers, crosslinking products and block copolymers ofthe above-mentioned polymers.

Known methods can be applied to the preparation of the vinyl chloridecompositions of the invention. Examples of the method for thepreparation thereof include

a method wherein the vinyl chloride resin component [A],

the cycloolefin ring opening polymer or copolymer, or hydrogenatedproduct thereof [B], and

the cycloolefin random copolymer [C], and if desired other componentsare mechanically blended by an extruder, kneader, etc.,

a method wherein the components mentioned above are simultaneouslydissolved into a suitable good solvent, for example, a hydrocarbonsolvent such as hexane, heptane, decane, cyclohexane, benzene, tolueneor xylene or the components are each separately dissolved into separatesolvents and the resultant solutions are mixed, and the solvent orsolvents are removed, and

a method wherein these two methods are combined.

The vinyl chloride resin compositions according to the present inventioncontain a cycloolefin polymer having a high heat distortion temperature,a high pencil hardness and a low mold shrinkage factor in addition tothe vinyl chloride resin component [A]. Accordingly, the resulting vinylchloride resin composition has a high heat distortion temperature whilemaintaining various characteristics of the vinyl chloride resin.

The vinyl chloride resin compositions according to the present inventionhave various characteristics as described above, and therefore can beextensively used in the field requiring heat-resistant properties inaddition to the field where conventional vinyl chloride resin is used.

MOLDED ARTICLES

Molded articles formed from the vinyl chloride resin compositionsaccording to the present invention have an excellent balance among heatresistance, heat aging characteristics, mechanical properties,dielectric properties, chemical resistance and solvent resistance.Concrete examples of the molded articles include

(1) automobile parts:

instrument panels, console boxes, meter clusters, column covers, grilledoor mirrors, fenders, bonnets and radiator grilles;

(2) machine housings:

tools (e.g., electric tools), business machines (e.g., word processors,personal computers, copying machines, printers, FDD and CRT), precisioninstruments (e.g., cameras) and electrical appliances (e.g., electronicovens, electric rice cookers, refrigerators, pots and cleaners); and

(3) machine parts:

scirocco fans for air conditioners.

The vinyl chloride resin compositions according to the present inventioncan be molded into molded articles by extrusion molding, injectionmolding, blow molding, rotary molding, etc. using, for example, a singlescrew extruder, a vented extruder, a twin screw extruder, a conical twinscrew extruder, a Ko-kneader, a platificator, a mixtruder, a twinconical screw extruder, a planetary screw extruder, a gear extruder anda screwless extruder.

EFFECT OF THE INVENTION

The vinyl chloride resin compositions according to the present inventioncomprise a vinyl chloride resin and a cycloolefin polymer as illustratedabove. Accordingly, the present invention can provide vinyl chlorideresin compositions from which molded articles required to have heatresistance as well as flame retarding properties and chemical resistancecan be prepared without losing the characteristics of polyvinylchloride.

EXAMPLES

The present invention is further illustrated below with reference toexamples, but it should be construed that the present invention is in noway limited to these examples.

Methods for measuring various physical properties and evaluation methodsof the resin compositions of the present invention are described below.

(1) Preparation of test pieces

Resin compositions are molded into test pieces under the followingconditions using an injection molding machine (trade name of IS-35P,manufactured by Toshiba Kikai K.K.):

a cylinder temperature of 220° C.;

a mold temperature of 60° C.;

primary injection/secondary injection pressures of 1000/800 kg/cm² ;

an injection speed (primary) of 30 mm/sec;

a screw rotation speed of 150 rpm; and

a cycle [(injection+dwell)/cooling] of 7/15 sec.

The test pieces are then allowed to stand at room temperature for 48hours, and used for measurements.

(2) Melt flow rate (MFR_(T))

The met flow rate is measured according to ASTM D 1238 at apredetermined temperature of T° C. under a load of 2.16 kg.

(3) Tensile test

The tensile test was conducted according to ASTM D 638 under thefollowing conditions:

the shape of the test pieces: ASTM Type IV, with a thickness of 2 mm;

a test speed of 50 mm/min; and

a test temperature of 23° C.

(4) Heat deflection temperature (HDT)

The heat deflection temperature is measured according to ASTM D 648under the following conditions:

the shape of the test piece: 5×1/4×1/2^(t) inch; and a load of 264 psi.

(5) Softening temperature (TMA)

The softening temperature is measured by observing the thermaldeformation behavior of a sheet of 1 mm thick using a Thermo MechanicalAnalyzer (trade name, manufactured by DuPont). That is, a quartz needleis placed on the sheet, and the sheet was heated at a rate of 5° C./minwhile a load of 49 g is applied to the needle. The TMA is a temperatureat which the needle penetrates the sheet to the depth of 0.635 mm.

(6) Glass transition temperature (Tg)

The glass transition temperature is measured by heating the test pieceat a rate of 10° C./min using DSC 20 (trade name, manufactured by SeikoDenshi Kogyo K.K.).

(7) Flame retardance

The flame retardance of the test piece having 1/8 inch thick is measuredaccording to the test method of UL-94.

EXAMPLE 1

A powder mixture (3 kg) of 100 parts by weight of a polyvinyl chloride(polymerization degree of 720, MFR₁₉₀ of 360 g/10 min, glass transitiontemperature Tg of 68° C.), and 3 parts by weight of tribasic leadsulfate and 1 part by weight of lead stearate as stabilizers was mixedwith 1 kg of pellets prepared from a mixture of 100 parts by weight of arandom copolymer as a cycloolefin polymer component of ethylene and1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene ##STR19##abbreviated to DMON hereinafter) as a cycloolefin polymer component(ethylene content of 62 mol% as measured by ¹³ C-NMR, MFR₂₆₀ of 35g/min, intrinsic viscosity [η] of 0.47 dl/g as measured in deoalin at135° C., softening temperature (TMA) of 148° C., glass transitiontemperature Tg of 137° C.) and 0.5 part by weight oftetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methaneas a stabilizer. The mixture was melt blended by a twin-screw extruder(trade name of PCM 45, manufactured by Ikegai Tekko K.K.) at a cylindertemperature of 170° C., and pelletized by a pelletizer. Test pieces wereprepared from the pellets thus obtained by the method mentioned above,and the physical properties thereof were measured.

The results are shown in Table 1.

EXAMPLE 2

Example 1 was repeated except that the same polyvinylchloride-containing powder and the same cycloolefin copolymer-containingpellets as in Example 1 were used in the proportion by weight of 1/1 tomelt blend and obtain test pieces. The physical properties of the testpieces were measured.

The results are shown in Table 1.

EXAMPLE 3

Example 1 was repeated except that the same polyvinylchloride-containing powder and the same cycloolefin copolymer-containingpellets as in Example 1 were used in the proportion by weight of 1/3,and that 15 parts by weight of antimony trioxide and 1 part by weight ofpolytetrafluoroethylene powder were added as flame retarding assistantsto 100 parts by weight of the mixture of pellets to melt blend andobtain test pieces. The physical properties of the test pieces weremeasured.

The results are shown in Table 1.

COMPARATIVE EXAMPLE 1

Test pieces were prepared by using only the same polyvinyl chloride asin Example 1, and the physical properties thereof were measured.

The results are shown in Table 1.

EXAMPLE 4

Example 1 was repeated except that a vinyl chloride/vinyl acetatecopolymer containing 5 mol% of vinyl acetate (polymerization degree of750, MFR₁₉₀ of 370 g/10 min, glass transition temperature Tg of 58° C.)was used in place of the polyvinyl chloride in Example 1, and 3 kg ofthe powder containing this copolymer and 1 kg of the same cycloolefincopolymer-containing pellets were mixed to obtain test pieces. Thephysical properties of the test pieces were measured.

The results are shown in. Table 1.

COMPARATIVE EXAMPLE 2

Test pieces were prepared by using only the same vinyl chloride/vinylacetate copolymer as in Example 4, and the physical properties weremeasured.

The results are shown in Table 1.

EXAMPLE 5

Example 1 was repeated except that an ethylene/DMON copolymer (ethylenecontent of 71 mol% as measured by ¹³ C-NMR, MFR₂₆₀ of 20 g/10 min,intrinsic viscosity [η] of 0.6 dl/g, softening temperature (TMA) of 115°C., glass transition temperature Tg of 98° C.) was used in place of theethylene/DMON copolymer in Example 1, and 1 kg of the pellets containingthis cycloolefin copolymer was mixed with 3 kg of the same polyvinylchloride containing powder to obtain test pieces. The physicalproperties of the test pieces were measured.

The results are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                                   Polyvinyl Tensile                                                             chloride/ strength                                                            copolymer at break HDT   Flame                                     Example    (wt. ratio)                                                                             (kg/cm.sup.2)                                                                          (°C.)                                                                        retardance                                ______________________________________                                        Example 1  75/25     530      80    V-O                                       Example 2  25/75     490      100   V-O                                       Example 3  25/75     540      125   V-O                                       Comp. Example 1                                                                          100/0     520      70    V-O                                       Example 4  75/25     490      70    V-O                                       Comp. Example 2                                                                          100/0     510      60    V-O                                       Example 5  75/25     550      75    V-O                                       ______________________________________                                    

I claim:
 1. A vinyl chloride resin composition comprising:(1) (A) avinyl chloride resin having a polymerization degree of 200 to 5,000, aglass transition temperature (Tg) of 40° to 90° C. and a melt flow rateof 0.1 to 500 g/10 min as measured at 190° C. under a load of 2.16 kg;and (2) (B) a hydrogenated product of a cycloolefin ring opening polymeror copolymer formed by ring opening polymerization of a cycloolefinrepresented by the following formula (I), said hydrogenated producthaving an intrinsic viscosity (η), as measured in decalin at 135° C., of0.1 to 7 dl/g and a melt flow rate of 0.01 to 150 g/10 min as measuredat 260° C. under a load of 2.16 kg, and/or (C) a cycloolefin randomcopolymer of ethylene and a cycloolefin represented by the followingformula (I), said copolymer having an intrinsic viscosity (η), asmeasured in decalin at 135° C., of 0.05 to 10 dl/g and a glasstransition temperature (Tg) of at least 70° C.; wherein the formulationratio by weight of the total amount of the hydrogenated product of thecycloolefin ring opening polymer or copolymer (B) and the cycloolefinrandom copolymer (C) to the amount of the vinyl chloride resin (A) (((B)+(C))/(A) ) is 75/25 to 5/95; ##STR20## wherein n is 0 or 1, m is 0or a positive integer, providing m+n≧1, R¹ -R¹⁸ are each independently ahydrogen, a halogen or a hydrocarbon group, with the proviso that R¹⁵-R¹⁸, linked together, may form a monocyclic ring or polycyclic ringwhich may have a double bond, and with the further proviso that R¹⁵ andR¹⁶ or R¹⁷ and R¹⁸ may together form an alkylidene group.
 2. A vinylchloride resin composition comprising:(1) (A) a vinyl chloride resinhaving a polymerization degree of 200 to 5,000, a glass transitiontemperature (Tg) of 40° to 90° C. and a melt flow rate of 0.1 to 500g/10 min as measured at 190° C. under a load of 2.16 kg; and (2) (B) ahydrogenated product of a cycloolefin ring opening polymer or copolymerformed by ring opening polymerization of a cycloolefin represented bythe following formula (I), said hydrogenated product having an intrinsicviscosity (η), as measured in decalin at 135° C., of 0.1 to 7 dl/g and amelt flow rate of 0.01 to 150 g/10 min as measured at 260° C. under aload of 2.16 kg, and/or (C) a cycloolefin random copolymer of ethyleneand a cycloolefin represented by the following formula (I), saidcopolymer having an intrinsic viscosity (η), as measured in decalin at135° C., of 0.05 to 10 dl/g and a glass transition temperature (Tg) ofat least 70° C.; (3) at least one stabilizer selected from the groupconsisting of lead salts, metallic soaps and organotin compounds;whereinthe formulation ratio by weight of the total amount of the hydrogenatedproduct of the cycloolefin ring opening polymer or copolymer (B) and thecycloolefin random copolymer (C) to the amount of the vinyl chlorideresin (A) ( ((B)+(C))/(A) ) is 75/25 to 5/95; ##STR21## wherein n is 0or 1, m is 0 or a positive integer, providing m+n≦1, R¹ -R¹⁸ are eachindependently a hydrogen, a halogen or a hydrocarbon group, with theproviso that R¹⁵ -R¹⁸, linked together, may form a monocyclic ring orpolycyclic ring which may have a double bond, and with the furtherproviso that R¹⁵ and R¹⁶ or R¹⁷ and R¹⁸ may together form an alkylidenegroup.
 3. A vinyl chloride resin composition comprising:(1) (A) a vinylchloride resin having a polymerization degree of 200 to 5,000, a glasstransition temperature (Tg) of 40° to 90° C. and a melt flow rate of 0.1to 500 g/10 min as measured at 190° C. under a load of 2.16 kg; and (2)(B) a hydrogenated product of a cycloolefin ring opening polymer orcopolymer formed by ring opening polymerization of a cycloolefinrepresented by the following formula (I), said hydrogenated producthaving an intrinsic viscosity (η), as measured in decalin at 135° C., of0.1 to 7 dl/g and a melt flow rate of 0.01 to 150 g/10 min as measuredat 260° C. under a load of 2.16 kg, and or (C) a cycloolefin randomcopolymer of ethylene and a cycloolefin represented by the followingformula (I), said copolymer having an intrinsic viscosity (η), asmeasured in decalin at 135° C., of 0.05 to 10 dl/g and a glasstransition temperature (Tg) of at least 70° C.; (3) at least onestabilizer selected from the group consisting of lead salts, metallicsoaps and organotin compounds; and (4) at least one stabilizer selectedfrom the group consisting of phenolic antioxidants and aliphatic acidesters of polyhydric alcohols; wherein the formulation ratio by weightof the total amount of the hydrogenated product of the cycloolefin ringopening polymer or copolymer (B) and the cycloolefin random copolymer(C) to the amount of the vinyl chloride resin (A) ( ((B)+(C))/(A) ) is75/25 to 5/95; ##STR22## wherein n is 0 or 1, m is 0 or a positiveinteger, providing m+n≦1, R¹ -R¹⁸ are each independently a hydrogen, ahalogen or a hydrocarbon group, with the proviso that R¹⁵ -R¹⁸, linkedtogether, may form a monocyclic ring or polycyclic ring which may have adouble bond, and with the further proviso that R¹⁵ and R¹⁶ or R¹⁷ andR¹⁸ may together form an alkylidene group.